Regenerable sorbent for carbon dioxide removal

ABSTRACT

A mixed salt composition adapted for use as a sorbent for carbon dioxide removal from a gaseous stream is provided, the composition being in solid form and including magnesium oxide, an alkali metal carbonate, and an alkali metal nitrate, wherein the composition has a molar excess of magnesium characterized by a Mg:X atomic ratio of at least about 3:1, wherein X is the alkali metal. A process for preparing the mixed salt is also provided, the process including mixing a magnesium salt with a solution comprising alkali metal ions, carbonate ions, and nitrate ions to form a slurry or colloid including a solid mixed salt including magnesium carbonate; separating the solid mixed salt from the slurry or colloid to form a wet cake; drying the wet cake to form a dry cake including the solid mixed salt; and calcining the dry cake to form a mixed salt sorbent.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional application of U.S. application Ser. No.14/415,283, filed on Jan. 16, 2015, which is a national stage filingunder 35 U.S.C. 371 of PCT/US2013/051257, filed Jul. 19, 2013, whichInternational Application was published by the International Bureau inEnglish on Jan. 23, 2014, and claims priority from U.S. ProvisionalApplication No. 61/673,626, filed on Jul. 19, 2012, which applicationsare hereby incorporated in their entirety by reference in thisapplication.

FIELD OF THE INVENTION

The invention relates to a regenerable solid sorbent material suitablefor CO₂ capture from a gaseous stream, particularly exhaust gas streamscharacterized by relatively high temperatures and relatively low CO₂partial pressures, as well as processes and systems using such a sorbentand methods of making such a sorbent.

BACKGROUND OF THE INVENTION

Combustion of fossil fuels is reported to be a major cause of theincreased concentration of carbon dioxide (CO₂) in the atmosphere.Although research is ongoing to improve energy efficiency and tosubstitute low-carbon fuels to combat this problem, these methods willlikely be insufficient to limit the growth of atmospheric CO₂concentrations to an acceptable level. As a result, there is tremendousinterest in the development of methods for preventing CO₂ release intothe atmosphere, i.e., carbon capture and storage (CCS) technology.

A number of technologies are available for removing CO₂ from a gaseousstream, including wet chemical absorption with a solvent (e.g., usingamines such as monoethanolamine or diethanolamine), membrane separation,cryogenic fractionation, and adsorption using molecular sieves. Anothermethod for the removal of CO₂ from a gas stream involves dry scrubbing,meaning treatment of the process gas with a dry, regenerable sorbentthat removes CO₂ by chemical absorption/adsorption.

Existing technologies for CO₂ capture from gaseous streams suffer from anumber of drawbacks. The Department of Energy has reported that existingCO₂ capture technologies are not cost-effective when considered in thecontext of large power plants. The net electricity produced fromexisting plants would be significantly reduced upon implementation ofmany of these CO₂ capture technologies, since a high percentage of thepower generated by the plant would have to be used to capture andcompress the CO₂. Additionally, the process conditions under which theCO₂ must be removed in many applications render the existingtechnologies unusable. For example, exhaust gas streams includingautomotive exhaust, cement kiln flue gas, steel mill flue gas, dieselgenerator exhaust, and many other industrial and process gas streams aresimply too hot (up to 600° C.) for conventional post-combustion CO₂capture technologies. Still further, the CO₂ partial pressure of thesegas streams is too low, typically less than 14.7 psia CO₂, for naturalgas sweetening or syngas CO₂ capture technologies to be effective. Thecombination of high temperatures and low CO₂ partial pressures makes thedevelopment of a material capable of effectively removing CO₂ from thesegas streams a significant challenge.

U.S. Pat. Nos. 5,480,625 and 5,681,503 are directed to sorbents forremoving carbon dioxide from habitable enclosed spaces, the sorbentsincluding a metal oxide (e.g., silver oxide) as the active agent and analkali metal carbonate. However, the only exemplified sorbentregeneration temperature range given is 160-220° C., too low to beuseful for most exhaust gas applications.

U.S. Pat. No. 6,280,503 describes a solid sorbent comprising magnesiumoxide, preferably promoted with an alkali metal carbonate or alkalimetal bicarbonate, for removal of CO₂ from gas streams at temperaturesin the range of 300 to 500° C.

U.S. Pat. No. 6,387,337 describes a CO₂ capture system that utilizes asorbent in the form of an alkali metal compound or an alkaline-earthmetal compound, and that purportedly operates over a temperature rangeof 200 to 2000° F.

U.S. Pat. No. 6,387,845 is directed to a CO₂-absorbing sorbentcomprising lithium silicate optionally promoted by addition of an alkalimetal carbonate, and which is capable of operation at temperaturesexceeding about 500° C.

U.S. Pat. No. 7,314,847 is directed to a regenerable sorbent for CO₂capture that includes a binder in combination with one or more activecomponents selected from alkali metal oxide, alkali metal hydroxide,alkaline earth metal oxide, alkaline earth metal hydroxide, alkalititanate, alkali zirconate, and alkali silicate. The sorbents aredescribed as capable of operation over a temperature range of 25 to 600°C.

U.S. Pat. No. 8,110,523 describes a sorbent for CO₂ capture thatcomprises an alkali metal carbonate or bicarbonate combined with a highsurface area support and a binder. The patent suggests that the sorbentcan operate over a temperature range of 40-200° C.

There is a continuing need in the art for the development of a sorbentmaterial that is capable of effectively removing CO₂ from gaseousstreams, particularly exhaust gas streams characterized by relativelyhigh temperatures and relatively low CO₂ partial pressures.

SUMMARY OF THE INVENTION

The present invention provides a mixed salt composition adapted for useas a sorbent for carbon dioxide removal from a gaseous stream, thecomposition being in solid form and comprising i) magnesium oxide; ii)an alkali metal carbonate; and iii) an alkali metal nitrate, wherein thecomposition has a molar excess of magnesium characterized by a Mg:Xatomic ratio of at least about 1.1:1, wherein X is the alkali metal. Thesorbent is suitable for removing carbon dioxide from a wide range ofCO₂-containing gaseous streams, and is particularly well-suited for CO₂scrubbing of exhaust gases characterized by low CO₂ partial pressure andmoderately high temperature. In one embodiment, a pellet of the sorbentof the invention has a crush strength, as determined by the Shellmethod, of at least about 0.3 MPa.

In certain embodiments, the alkali metal comprises sodium. The Mg:Xatomic ratio can vary, but will often be at least about 4:1 or at leastabout 6:1. The alkali metal nitrate is typically present in an amount ofat least about 1% by weight, based on total dry weight of the mixed saltcomposition. An exemplary sorbent mixture is MgO:Na₂CO₃:NaNO₃.

The invention also provides a method for removing carbon dioxide from agaseous stream, comprising contacting a gaseous stream containing carbondioxide with a sorbent material comprising the mixed salt composition ofthe invention. In certain embodiments, the contacting step occurs at atemperature of about 100° C. to about 450° C. (e.g., about 250° C. toabout 375° C.) and a carbon dioxide partial pressure in the gaseousstream of about 1 to about 300 psia. In one embodiment, the gaseousstream has a low carbon dioxide partial pressure, such as less thanabout 20 psia (e.g., less than about 14 psia, less than about 10 psia,less than about 5 psia, or less than about 3 psia). In one embodiment,the sorbent material exhibits a CO₂ loading of at least about 10 weightpercent CO₂ at an absorption temperature of about 250 to about 350° C.

The type of absorber housing the sorbent of the invention is notparticularly limited, and can include, for example, either a fixed bedor fluidized bed absorber. The sorbent is regenerable, meaning thesorbent can be treated to cause desorption of carbon dioxide and reused.The regenerating step can vary, with exemplary regeneration processesincluding pressure-swing absorption, temperature-swing absorption, or acombination thereof. The regenerating step will often include raisingthe temperature of the sorbent material or lowering the pressure appliedto the sorbent material, as compared to the temperature and pressureduring the contacting step. In the case of pressure swing absorption,the total pressure may remain constant or near constant while thepartial pressure of CO₂ is lowered, such as by purging with steam.

In a further aspect, the invention provides a process for preparing themixed salt composition of the invention, the process comprising: mixinga magnesium salt with a solution containing alkali metal ions, carbonateions, and optionally nitrate ions, to form a slurry or colloidcomprising a solid mixed salt comprising magnesium carbonate; separatingthe solid mixed salt from the slurry or colloid to form a wet cake ofthe solid mixed salt; drying the wet cake to form a dry cake comprisingthe solid mixed salt; and calcining the dry cake to form a mixed saltcomposition according to the invention.

The mixing step can comprise mixing a first solution containing adissolved alkali metal carbonate, and optionally a dissolved alkalimetal nitrate, and a second solution containing a dissolved magnesiumsalt to form the solid mixed salt as a co-precipitate. In advantageousembodiments, the magnesium salt used in the co-precipitation process ishighly water soluble, such as magnesium salts having a water solubilityof at least about 10 g per 100 ml at 25° C. and one atmosphere, or atleast about 40 g per 100 ml. Exemplary water soluble magnesium saltsinclude magnesium nitrate, magnesium acetate, and magnesium chloride.The carbonate ions in the solution are typically derived from aprecipitating salt comprising a carbonate ion added to the solution(e.g., an alkali metal carbonate or ammonium carbonate).

Alternatively, the mixing step can include combining a solid magnesiumsalt (e.g., basic magnesium carbonate) with the solution to form thesolid mixed salt as a colloid. In one embodiment, a solid magnesium saltis combined with a solution containing a dissolved alkali metalcarbonate and a dissolved alkali metal nitrate to form the solid mixedsalt as a colloid.

BRIEF DESCRIPTION OF THE DRAWINGS

Having thus described the invention in general terms, reference will nowbe made to the accompanying drawings, which are not necessarily drawn toscale, and wherein:

FIG. 1 is a flow chart illustrating a process for using the sorbent ofthe invention to remove CO₂ from a gas stream;

FIG. 2 is an x-ray powder diffraction (XRD) pattern of a preparedsorbent according to the invention showing the desired MgO:Na₂CO₃:NANO₃composition;

FIG. 3 graphically illustrates the CO₂ loading characteristics atdifferent temperatures for the sorbent prepared in Example 1 using a lowCO₂ partial pressure feed gas;

FIG. 4 graphically illustrates the CO₂ loading characteristics atdifferent temperatures for the sorbent prepared in Example 2 using a lowCO₂ partial pressure feed gas;

FIG. 5 graphically illustrates the CO₂ loading characteristics at twotemperatures for the sorbent prepared in Example 1 using a feed gas ofvarying CO₂ partial pressure;

FIG. 6 graphically illustrates the effect of alkali metal selection onCO₂ loading characteristics of a sorbent according to the invention;

FIG. 7 graphically illustrates the effect of magnesium salt selection onCO₂ loading characteristics of a sorbent according to the invention;

FIG. 8 graphically illustrates the effect of Mg:Na atomic ratio in thereagent mixture on CO₂ loading characteristics of a sorbent according tothe invention;

FIG. 9 graphically illustrates the effect of precipitation solutionconcentration on CO₂ loading characteristics of a sorbent according tothe invention;

FIG. 10 graphically illustrates the effect of precipitating agentselection on CO₂ loading characteristics of a sorbent according to theinvention;

FIG. 11 graphically illustrates the effect of production method on CO₂loading characteristics of a sorbent according to the invention;

FIG. 12 graphically illustrates the effect of magnesium oxide source ina gelation production method on CO₂ loading characteristics of a sorbentaccording to the invention; and

FIG. 13 graphically illustrates the effect of drying process selectionon CO₂ loading characteristics of a sorbent according to the invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention now will be described more fully hereinafter withreference to the accompanying drawings, in which some, but not allembodiments of the inventions are shown. Indeed, these inventions may beembodied in many different forms and should not be construed as limitedto the embodiments set forth herein; rather, these embodiments areprovided so that this disclosure will satisfy applicable legalrequirements. Like numbers refer to like elements. As used in thespecification, and in the appended claims, the singular forms “a”, “an”,“the”, include plural referents unless the context clearly dictatesotherwise.

The present invention provides a mixed salt composition adapted for useas a sorbent for carbon dioxide removal from a gaseous stream, thecomposition being in solid form and comprising magnesium oxide; analkali metal carbonate; and an alkali metal nitrate, wherein thecomposition has a molar excess of magnesium characterized by a Mg:Xatomic ratio of at least about 1.1:1, wherein X is the alkali metal.Exemplary ranges of Mg:X atomic ratio include at least about 2:1, atleast about 3:1, at least about 4:1, at least about 5:1, at least about6:1, at least about 7:1, and at least about 8:1. Note that the twoalkali metal salts in the sorbent will typically comprise the samealkali metal (e.g., sodium), although mixtures of different alkalimetals could be used without departing from the invention. Oneembodiment of the sorbent of the invention is the mixtureMgO:Na₂CO₃:NaNO₃. Although not bound by a theory of operation, it isbelieved that the sorbent of the invention loads CO₂ in the form ofmagnesium carbonate (MgCO₃), while the alkali metal component of thesorbent promotes the reactions through which CO₂ is captured by thesorbent. Other acid gas components of a process gas stream can also beremoved using the sorbent of the invention, such as H₂S, COS, SO₂,NO_(X) species, and the like. In some cases, these acid gases may beirreversibly absorbed.

The relative amount of Mg and alkali metal can be characterized in termsof mass. In certain embodiments, the mixed salt sorbent comprises atleast about 60% by weight magnesium oxide (based on total dry weight ofthe mixed salt composition), more often at least about 70%, at leastabout 75%, or at least about 80% by weight magnesium oxide (e.g., a MgOweight range of about 70% to about 90%). In certain embodiments, themixed salt sorbent comprises at least about 8% by weight of alkali metalcarbonate (e.g., sodium carbonate), based on total dry weight of themixed salt composition, such as at least about 10% by weight, at leastabout 12% by weight, or at least about 14% by weight (e.g., an alkalimetal carbonate weight range of about 8% to about 18%). In certainembodiments, the mixed salt sorbent comprises at least about 1% byweight of alkali metal nitrate (e.g., sodium nitrate), based on totaldry weight of the mixed salt composition, such as at least about 2% byweight, at least about 3% by weight, or at least about 5% by weight(e.g., an alkali metal nitrate weight range of about 1% to about 10%).

As used herein, “magnesium salt” refers to an ionic compound comprisingmagnesium as a cation. “Alkali metal salt” refers to an ionic compoundcomprising an alkali metal as the cation. The alkali metal (i.e., aGroup 1 element, formerly known as Group IA elements) can vary, andexpressly includes lithium, sodium, potassium, rubidium, caesium, andfrancium. The anions associated with either the magnesium salts oralkali metal salts can vary, with specific examples including carbonate,acetate, chloride, hydroxide, oxide, and nitrate groups.

The mixed salt sorbent of the invention can be characterized by CO₂loading ability. Certain embodiments of the sorbent of the invention arecapable of achieving CO₂ loading of at least about 10 weight percentCO₂, at least about 15 weight percent CO₂, at least about 20 weightpercent CO₂, or at least about 25 weight percent CO₂ (e.g. about 10 toabout 30 weight percent CO₂). Although the composition of the sorbentcan impact peak absorption temperature, in one embodiment, theabove-noted CO₂ loading levels are achieved at an absorption temperaturein the range of about 250 to about 350° C.

The sorbent composition is typically used in a particulate form with aparticle size of about 150-425 mesh, although other particle size rangescould be used without departing from the invention. In certainembodiments, the sorbent composition can include additional components.For example the sorbent can include one or more inert binders forvarious purposes, such as to facilitate granulation or extrusion,improve handling, enhance particle strength, or reduce pressure dropacross packed sorbent beds. Exemplary binders include alkali silicates,inorganic clays, boehmite, and organic binders (e.g., starch, cellulosicpolymers such as methylcellulose, polyvinyl acetate, and ligninsulfonate). Binders used in the present invention should be chemicallystable at the operating temperature of the sorbent (e.g., about 100 toabout 450° C.). In some cases, certain binders are detrimental to theperformance of the sorbent. For example, it has been determined that theuse of boehmite is generally disadvantageous because the presence ofboehmite reduces CO₂ loading performance, presumably due to interactionbetween the alkali metal promoter of the sorbent and the boehmite.

Certain binders, such as methylcellulose, can impart porosity to thefinal sorbent composition. Organic binders of this type are removedduring the calcinations step, leaving a pore network within the sorbentextrudate.

Although some binder materials can also enhance particle strength ofsorbents, it has been determined that the sorbent of the invention maynot require a binder to enhance particle strength because the crushstrength of the sorbent of the invention made without binder was foundto be approximately equivalent to a sorbent composition of the inventionthat included a boehmite binder. The crush strength of a pellet (i.e.,extrudate) of the sorbent of the invention, as determined by the Shellmethod, is typically at least about 0.3 MPa, at least about 0.4 MPa, orat least about 0.5 MPa (e.g., a crush strength range of about 0.3 MPa toabout 1 MPa).

The sorbent composition of the invention can further include a porousmaterial as a carrier for the mixed salt composition. Exemplary porouscarriers include bauxite, activated carbon, clays (e.g., amorphous,crystalline, or mixed layer clays), metal oxides (e.g., iron oxide,alumina, magnesium oxide, and zirconium oxide), magnesium silicate,molecular sieves, silica gel, and zeolites.

Although the sorbent of the invention has a large molar excess of Mgover alkali metal, the initial reagent mixture used to produce the finalproduct will typically exhibit a molar excess of alkali metal. As thealkali metal is more soluble in water, more of the alkali metal willremain in solution during the reactions that lead to formation of thefinal mixed salt composition, and more alkali metal is lost during stepstaken to effect separation of the solid mixed salt from the solution(e.g., filtration or washing steps).

As shown in Example 9, the extent of the molar excess of the alkalimetal over the magnesium in the initial reagent mixture used in theco-precipitation method can vary, and will impact the level of CO₂loading and optimal absorption temperature for the sorbent. Greateralkali metal content in terms of Mg:X atomic ratio, such as greater thanabout 1:3, greater than about 1:4, greater than about 1:5, greater thanabout 1:6, greater than about 1:7, or greater than about 1:8, tend toincrease both the maximum CO₂ loading capacity of the sorbent as well asthe optimal absorption temperature. Lower molar excesses may beappropriate where a lower absorption temperature is desirable. A typicalmolar excess range for the co-precipitation method is an Mg:X ratio ofabout 1:3 to about 1:10 for the initial reagent mixture.

The mixed salt sorbent compositions of the invention can be made by anyprocess that facilitates formation of a solid mixed salt from solution(e.g., co-precipitation or gelation/colloid processes). The salts usedin the process are chosen such that, upon reaction, MgCO₃ is formed inthe precipitate. The process of the invention will typically involvemixing a magnesium salt and an alkali metal salt in the presence ofcarbonate and nitrate ions in solution. The carbonate ions are typicallyprovided by a precipitating agent in order to drive formation of thedesired magnesium salt. The precipitating agent and the alkali metalsalt can be the same reagent in some embodiments, meaning the alkalimetal salt is a carbonate salt, thereby providing both the necessaryalkali metal content and carbonate ions. In a typical co-precipitationprocess, both the magnesium salt and the alkali metal salts are providedin a dissolved form and the solutions of each salt are combined andmixed, which produces the desired precipitate of the mixed salt sorbentof the invention. The mixing step typically comprises mixing a firstsolution containing dissolved alkali metal carbonate and nitrate salts(e.g., sodium carbonate and sodium nitrate) and a second solutioncontaining a dissolved magnesium salt (e.g., magnesium nitrate) to formthe solid mixed salt of the invention as a co-precipitate.

The carbonate ions in the solution are derived from a precipitating saltcomprising a carbonate ion added to the solution. As noted above, thealkali metal salt itself can be the source of carbonate ions (e.g.,sodium carbonate), or other sources of carbonate ions can be used inaddition to the alkali metal salt (e.g., ammonium carbonate). At leastone of the salts mixed in the mixing step is a nitrate salt and at leastone of the salts mixed in the mixing step is a carbonate salt. Inaddition to reagent-grade alkali metal salts that are commerciallyavailable, commercial-grade reagents can also be used in some cases,such as the use of soda ash as a sodium carbonate source.

As noted in Example 8 below, the water solubility of the magnesium saltused in the co-precipitation process can have a significant impact onthe performance of the sorbent, both in terms of maximum CO₂ loading andoptimal absorption temperature. The use of magnesium salts with higherwater solubility levels enhance CO₂ loading. In certain embodiments, thewater solubility of the magnesium salt is at least about 10 g per 100 ml(at 25° C. and one atmosphere), or at least about 40 g per 100 ml.Exemplary water soluble magnesium salts include magnesium nitrate,magnesium acetate, and magnesium chloride.

Co-precipitation processes where each salt is initially in solution canbe difficult to scale up because of the large quantity of solventrequired. Accordingly, in certain embodiments, the mixed salt sorbent isformed by a process where at least one of the salt components (typicallythe magnesium salt) is added in solid form to a solution of the othersalts (typically the alkali metal salts), resulting in colloidalgelation of the desired mixed salt sorbent of the invention. Such aprocess forms a stable colloid of the desired solid mixed salt dispersedin the solution. It has been determined that the gelation processdescribed herein can be used to scale up production (e.g., to 300 gbatch size) of the sorbent of the invention without losing carbondioxide capture performance.

In one embodiment of the gelation process, a solid magnesium salt suchas basic magnesium carbonate (e.g., magnesium carbonate hydroxide havingthe formula 4MgCO₃.Mg(OH)₂×H₂O), which is essentially water-insoluble,is mixed with a solution containing alkali metal ions, carbonate ions,and nitrate ions. The solution will typically comprise a dissolvedalkali metal carbonate (and/or other carbonate ion sources) and adissolved alkali metal nitrate. Mixing the solid magnesium salt with thedissolved alkali metal solution results in liquid-solid reactions, andultimately, formation of a stable colloid of the desired mixed saltsorbent material dispersed in the solution. In the gelation process, theformation of the desired mixed salt product proceeds in a manner similarto a sol-gel process, with the mixed salt product forming as adispersed, stable colloidal phase or network within the solution. It isnoted that the manner in which the solid magnesium salt is contactedwith the solution of alkali metal ions, carbonate ions, and nitrate ionscan vary. Powders of the magnesium salt and various alkali metal salts(e.g., sodium carbonate and sodium nitrate) can be premixed in dry formusing milling/grinding techniques known in the art and then combinedwith water to create the desired solution. Alternatively, the solutionof alkali metal ions, carbonate ions, and nitrate ions can be preparedfirst, followed by addition of the solid magnesium salt.

In either a colloid or co-precipitation process, the process stepstypically involve:

-   -   i) mixing a magnesium salt with a solution containing alkali        metal ions, carbonate ions, and nitrate ions to form a slurry or        colloid comprising a solid mixed salt, wherein the mixture of        the alkali metal salt with the magnesium salt in solution has a        molar excess of alkali metal characterized by a Mg:X atomic        ratio of at least about 1:3, wherein X is the alkali metal;    -   ii) separating the solid mixed salt from the slurry or colloid        to form a wet cake of the solid mixed salt;    -   iii) drying the wet cake to form a dry cake comprising the solid        mixed salt; and    -   iv) calcining the dry cake to form a mixed salt sorbent        composition according to the invention.

The separating and drying steps can be conducted using any conventionalseparation and drying equipment and techniques known in the art. Typicalseparating steps include centrifugation and/or filtration, optionallyaccompanied by one or more washing steps. Exemplary drying equipmentincludes spray dryers, rotary dryers, flash dryers, conveyer dryers,fluid bed dryers, and the like. The temperature and time of the dryingstep can vary, depending on the desired moisture content of the driedcake. A typical temperature range is about 50° C. to about 150° C. and atypical drying time is about 2 to about 24 hours.

Following drying, the dried cake is preferably subjected to a calciningstep. This step enhances the CO₂ loading capacity of the sorbent.Calcining temperatures and times can vary depending on the desired finalcharacteristics of the sorbent, but will typically involve a maximumtemperature in the range of 400 to 500° C. and a time of about 2 toabout 10 hours. The calcining is conducted by ramping up the temperatureof the sorbent at a ramp rate of, for example, about 1 to about 5° C.per minute. Following calcining, the mixed salt composition will be indry powder form. The particle size of the powder can be adjusted asdesired using milling or grinding equipment known in the art.

The sorbent powder can also be optionally combined with a binder andextruded before final processing into the desired granule size. Theextruding step can also occur before calcination so that thecalcinations process drives off any organic binder material present inthe final sorbent extrudate. Still further, the sorbent powder can beadmixed with a porous carrier using known techniques in the art, such asby mixing the porous carrier with a slurry of the sorbent powderfollowed by drying of the treated carrier. In addition, the sorbentmaterial can be slurried and spray-dried to form fluidizable particles.

If a sorbent extrudate is formed, the drying procedure used for theextrudate can impact the crush strength of the extrudate pellet. Crushstrength declines with increases in drying rate. Accordingly, allowingthe extrudate to remain at room temperature before subjecting thesorbent to higher temperatures is advantageous. Further, lower ramprates during drying are useful to reduce the impact of drying on crushstrength, such as temperature ramp rates of less than about 0.5° C./min,or less than about 0.4° C./min, or less than about 0.3° C./min.

The mixed salt sorbent composition of the invention can be used toremove carbon dioxide from a gaseous stream by contacting a gaseousstream containing carbon dioxide with a sorbent material comprising themixed salt composition of the invention for a time and at a temperaturesufficient for the sorbent to remove all or a portion of the CO₂ fromthe process gas stream. The process of using the sorbent is set forthschematically in FIG. 1. A process gas containing CO₂ is received instep 10 and contacted with the sorbent of the invention in step 20. Atreated process gas having a reduced CO₂ content can be withdrawn instep 30. The sorbent will eventually become saturated with CO₂ andrequire regeneration as noted in step 40, which usually involves passingan inert gas through the sorbent and changing the temperature orpressure conditions of the sorbent to facilitate desorption of CO₂ fromthe sorbent. The regeneration step may result in production of aconcentrated CO₂ gaseous stream in step 50. However, if a high qualityCO₂ product gas is not desired, a highly diluted CO₂ gaseous stream maybe produced by purging with a hot gas such as steam or air or anotherdiluent.

The process gas to be treated according to the invention can vary. Anygaseous mixture comprising CO₂ where it is desired to reduce the CO₂concentration of the gaseous mixture would be suitable for use in thepresent invention. Exemplary process gases include any exhaust gas froma fossil fuel combustion process (e.g., exhaust flue gas streamsproduced by fossil fuel-fired power plants including industrial boilers,exhaust from vehicles with internal combustion engines, cement kiln fluegas, steel mill flue gas, glass manufacturing flue gas, and dieselgenerator exhaust) or a syngas produced by the gasification of coal orreforming of natural gases. The sorbent of the invention could be used,for example, in advanced power systems such as Integrated GasificationCombined Cycle (IGCC), Low-Emissions Boiler Systems (LEBS), HighPerformance Power Systems (HIPPS), and Pressurized Fluid Bed Combustors(PFB).

Of particular interest are chemical conversion processes in which CO₂ isan undesirable by-product or a contaminant, such as the conversion ofwarm syngas to hydrogen, such as in the context of hydrogen productionfrom syngas derived from coal, biomass, or natural gas for powergeneration (for example in a gas turbine); hydrogen production forchemical conversions such as ammonia; or syngas production with desiredratio of H₂-to-CO for production of methanol and Fischer Tropschproducts. Incorporating the sorbent of the invention into a syngastreatment process could consist of stand-alone CO₂ removal from syngas,water-gas shift of syngas followed by CO₂ removal using the sorbent ofthe invention, or simultaneous water-gas shift of syngas and CO₂ removalknown as sorption-enhanced water-gas shift. Additional uses of thesorbent of the invention could include use in the process of directconversion (i.e., reforming and partial oxidation) of carbonaceous fuelsto hydrogen and syngas, or CO₂ scrubbing of recycle streams in chemicalconversion processes, such as recycle streams involved in ethylene oxideproduction, oxidative coupling of methane and ethane, or dimethyl etherproduction.

The partial pressure of CO₂ in the process gas to be treated with thesorbent of the invention can vary. A typical CO₂ partial pressure rangefor the process gas is about 1 to about 300 psia. In one embodiment, asexemplified in Example 5, the sorbent is effective at removing CO₂ fromgaseous streams characterized by high temperature (e.g., greater thanabout 400° C. or greater than about 425° C.) and high partial pressureof CO₂ (e.g., greater than about 30 psia, greater than about 50, orgreater than about 80 psia). However, the sorbent of the invention isalso effective at process conditions associated with many types ofexhaust gases; namely, moderately high temperatures (e.g., about 100 toabout 450° C., more typically about 250° C. to about 375° C.) and lowCO₂ partial pressure (e.g., less than about 20 psia, less than about 14psia, less than about 10 psia, or less than about 5 psia, or less thanabout 3 psia).

The manner in which the sorbent material is contacted with the processgas can vary. Typically, the sorbent is housed within an absorber in abed and the process gas passes through the bed. The bed of sorbent canbe in a fixed bed or fluidized bed configuration using absorber andregenerator designs known in the art. If a fixed bed of sorbent is used,the system may include multiple sorbent beds in parallel arrangementsuch that beds in need of regeneration can be taken offline andregenerated. In this embodiment, the same vessel is used as both anabsorber and a regenerator by simply changing the gas flowing throughthe vessel as well as the temperature and/or pressure in the vessel. Inanother embodiment, a fluidized bed of sorbent is used, and a separateabsorber and regenerator in fluid communication can be used. In thisembodiment, CO₂ loaded sorbent travels from the absorber to a separateregenerator vessel where CO₂ is stripped from the sorbent before thesorbent is transported back to the absorber in a continuous orsemi-continuous flow.

The method used to regenerate the sorbent will vary, but will usuallyinvolve changing the temperature or pressure experienced by the bed ofsorbent to facilitate release/desorption of the CO₂ bound in the mixedsalt composition. Known methods of regenerating sorbents can be used,such as pressure-swing absorption (PSA), including vacuum swingabsorption, temperature-swing absorption (TSA), or a combination thereof(e.g., combined TSA-PSA processes). Such regenerating processes involveone or more of raising the temperature or lowering the pressure appliedto the sorbent to desorb CO₂ into an inert gas (e.g., nitrogen or steam)passing through the sorbent bed. In certain embodiments, the sorbent ofthe invention is capable of regeneration at a temperature of about 375to about 450° C.

The sorbent will eventually become saturated with CO₂, and the level ofCO₂ loading in the sorbent material can be determined by measuring andcomparing the content of CO₂ in the process gas stream before and aftercontact with the sorbent. When it is evident that no further CO₂ isbeing removed from the process gas stream, the sorbent can beregenerated by, e.g., heating it to the desorption temperature. Bymeasuring the amount of CO₂ contained in the concentrated CO₂ gas streamexiting the regenerating sorbent, the skilled artisan can determine whenthe sorbent is ready for reuse. The CO₂ gaseous stream produced bysorbent regeneration can be sequestered as known in the art or used as araw material in processes requiring CO₂, such as in production ofvarious chemicals; as a component of fire extinguishing systems; forcarbonation of soft drinks; for freezing of food products; forenhancement of oil recovery from oil wells; and for treatment ofalkaline water.

EXAMPLES Example 1: Sorbent Prepared by Gelation

A sorbent comprising MgO:Na₂CO₃:NaNO₃ at a mass ratio of 75.8:16:8.2 wasprepared as follows. An amount (395 g) of magnesium carbonate hydroxide(4MgCO₃.Mg(OH)₂×H₂O) was added to 800 ml of a solution of sodiumcarbonate (42.18 g) and sodium nitrate (21.63 g) dissolved in deionizedwater. The resulting mixed salt colloid was stirred for 30 minutes,covered, and allowed to sit overnight (up to 16 hours) at ambienttemperature. Thereafter, the colloid was dried in an oven at 120° C.overnight (up to 16 hours) to form a dry cake.

The dry cake was then calcined by heating from 120° C. to 450° C., at aramp rate of 3° C./minute, followed by holding at a temperature of 450°C. for 4 hours. The calcined cake was crushed and sieved to collect a150-425 mesh fraction.

Example 2: Sorbent Prepared by Co-Precipitation

A magnesium-sodium mixed salt sorbent was prepared by precipitating asolid from two starting solutions. A first solution containing 233.4 gof Na₂CO₃ dissolved in 3000 ml deionized water was placed in a 5.0 literplastic beaker, and stirred vigorously with a mechanical agitator. Asecond solution of 188.4 g Mg(NO₃)₂:6H₂O in 500 ml of deionized waterwas pumped into the first solution at a rate of approximately 30ml/minute. The resulting slurry was stirred for an hour and then coveredand stored overnight under ambient conditions. Thereafter, the slurrywas filtered using a vacuum-assisted Buchner funnel assembly to collecta wet precipitate cake. About 3200 ml of filtrate was collected and thendried in an oven at 120° C. for 24 hours to form a dry cake. The driedcake was then calcined, crushed and sieved as described in Example 1. Acombination of inductively coupled plasma (ICP) analysis and elementalanalysis (CHONS) was used to determine/estimate the molecular speciescomposition of the calcined material. The sorbent was found to have anapproximate mass composition of MgO:Na₂CO₃:NaNO₃ of 86.8:8.8:4.4 and aMg:Na molar ratio of 9.8:1. An XRD pattern was collected for thecalcined sorbent powder and the presence of MgO, Na₂CO₃, and NaNO₃ wasclearly observed, as shown in FIG. 2, verifying that the preparedsorbent had the desired MgO:Na₂CO₃:NaNO₃.

Example 3: Carbon Dioxide Loading of Sorbent of Example 1

The amount of CO₂ loaded on the sorbent of Example 1 was evaluated usinga simulated exhaust gas consisting of 13% CO₂, 13% H₂O, and balance N₂(i.e., an exhaust gas with a CO₂ partial pressure of 1.9 psia) using aconventional, packed-bed reactor system equipped with a Horiba NDIR CO₂analyzer to measure the concentration of CO₂ in the gas entering andexiting the reactor. The packed-bed reactor was loaded with 6 g of theprepared sorbent of Example 1 and a quantity of an inert, siliconcarbide (SiC), to occupy the additional reactor volume. The reactor wasthen heated to 450° C. at 10° C./min in flowing N₂ to activate thesorbent and was held at this temperature until the CO₂ concentration inthe reactor effluent dropped below 0.1%. The reactor was cooled to thelowest absorption temperature in flowing N₂. Once the reactor stabilizedat the desired absorption temperature, the composition of the simulatedfeed gas (13% CO₂, 13% H₂O, bal. N₂) was verified by the CO₂ analyzer.When the CO₂ concentration was stable, +/−0.1% from set point, for aminimum of 5 minutes, the simulated exhaust gas was fed to the reactorfeed. The CO₂ concentration of the reactor effluent was continuouslymeasured by the CO₂ analyzer and the absorption phase of the cycle wascontinued until the CO₂ concentration in the effluent reached 90% of thepreviously measured feed concentration. This corresponds to a 90%breakthrough. At this point, the feed gas was changed to pure N₂ and thetemperature for the reactor was ramped at 5° C./min to 450° C. Thereactor was maintained at 450° C. until the CO₂ concentration in thereactor effluent decreased below 0.1 vol %, or a period of 2 hours wasexceeded, indicating the completion of sorbent regeneration. The reactortemperature was then reduced to the desired absorption temperature, andthe absorption-regeneration procedure described above was repeated.

FIG. 3 indicates the amount of carbon dioxide loaded on the sorbent overa range of temperatures from 200 to 425° C. in 25° C. increments. Asshown, the test illustrates the effectiveness of the sorbent atabsorbing CO₂ over a wide temperature range with a maximum loading atapproximately 300° C.

Example 4: Carbon Dioxide Loading of Sorbent of Example 2

The CO₂ loading ability of the sorbent of Example 2 was analyzed usingthe same experimental process outlined in Example 3. FIG. 4 indicatesthe amount of carbon dioxide loaded on the sorbent of Example 2 over arange of temperatures from 100 to 425° C. As shown, the test illustratesthe effectiveness of the sorbent at absorbing CO₂ over a widetemperature range with a maximum loading at approximately 350° C.

Example 5: Carbon Dioxide Loading of Sorbent of Example 1 Using High CO₂Partial Pressure Process Gas

The mixed salt sorbent described Example 1 was evaluated for removal ofCO₂ from warm, high CO₂ partial pressure process gas streams. There arenumerous examples of industrially-relevant process gas streams that canbe described as warm, high CO₂ partial pressure process gas streams,such as desulfurized syngas, high-temperature and low-temperatureshifted syngas, and CO₂-containing hydrogen.

In this example, simple gas mixtures containing CO₂ and N₂ with variousCO₂ partial pressures were used to simulate warm, high CO₂ partialpressure process gas streams. CO₂ uptake and release measurements weremade using a conventional, packed-bed reactor equipped with a HoribaNDIR CO₂ analyzer to measure the concentration of CO₂ in the gasentering and exiting the reactor. The packed-bed reactor was loaded with4 g of the prepared sorbent of Example 1 and a quantity of an inertmaterial (silicon carbide) was intermixed with the sorbent to occupy theremaining reactor volume. The reactor was then heated to 450° C. at 10°C./min in approximately 100 ml/min of N₂ to activate the sorbent and washeld at this temperature until the CO₂ concentration in the reactoreffluent dropped below 0.1%. The reactor pressure was then elevated toand maintained at 300 psia by a pressure control valve locateddownstream of the reactor. The reactor was cooled to the desiredabsorption temperature typically ranging between 375° C. and 450° C.Once the reactor stabilized at the desired absorption temperature, thecomposition of the simulated warm process gas, containing CO₂ and N₂,was verified by the CO₂ analyzer positioned downstream of the pressurecontrol valve. When the CO₂ concentration was stable, +/−0.1% from setpoint, for a minimum of 5 minutes, the simulated process gas was fed tothe reactor.

The CO₂ partial pressures evaluated ranged from 15 psia to 150 psia. TheCO₂ concentration of the reactor effluent was continuously measured bythe CO₂ analyzer and the absorption phase of the cycle was continueduntil the CO₂ concentration in the effluent reached 90% of thepreviously measured feed concentration. This corresponds to a 90%breakthrough. The amount of CO₂ absorbed by the sorbent, the CO₂ uptake,was determined by integration of the difference between the mass flowrates of CO₂ entering and exiting the reactor. Once 90% breakthrough hadbeen reached, the feed gas was changed to either pure N₂ or a CO₂/N₂mixture having lower CO₂ content than used in the absorption stage. Thereactor temperature was either maintained at the absorption temperatureor reduced to a lower temperature. The reactor remained in theregeneration stage until the CO₂ concentration in the reactor effluentdecreased to <0.1 vol % greater than the CO₂ concentration in the feedstream. The reactor temperature and CO₂ concentration was then returnedto the desired absorption conditions and the experiment could berepeated.

Results provided in FIG. 5 report the CO₂ loading capacity of the Mg—Namixed salt sorbent as a function of CO₂ partial pressure and absorptiontemperature. Increasing the CO₂ partial pressure in the simulated warmprocess gas resulted in large increases in the CO₂ loading. In thisstudy, the maximum CO₂ partial pressure evaluated was 150 psia,corresponding to a 50-50 mixture of CO₂ and N₂ with a total pressure of300 psia. At this CO₂ partial pressure, the sorbent was capable ofloading 52.2 wt % CO₂ and 49.6 wt % CO₂ at 430° C. and 450° C.respectively. For CO₂ partial pressures <20 psia CO₂, the sorbent didnot absorb measureable quantities of CO₂ for either temperatureevaluated. The shape of the CO₂ loading curve, having a rapid decreasein CO₂ loading with decreasing CO₂ partial pressure below 100 psia, isvery promising for temperature-swing, pressure-swing, andpartial-pressure swing absorption process arrangements and processarrangements consisting of combinations of temperature and pressureswing. These results also indicate that embodiments of the sorbent ofthe invention are useful for high temperature, high CO₂ partial pressureapplications in addition to exhaust gas applications characterized bymore moderate temperatures and very low CO₂ partial pressures.

Example 6: Regeneration of Sorbent of Example 1

The maximum CO₂ partial pressure that can be realized in theregeneration off-gas at a prescribed temperature was determined. Inthese experiments, the sorbent of Example 1 was loaded with CO₂ at 450°C. and a CO₂ partial pressure of 150 psia using an experimental systemessentially as described in Example 5. The CO₂-loaded sorbent was thenregenerated by cooling from 450° C. to the desired regenerationtemperature without flow and once the desired temperature was reached,the feed gas was switched to 15 psia CO₂ balance N₂. The CO₂ content ofthe gas exiting the reactor was measured by a downstream NDIR CO₂analyzer. Results presented in the table below report the maximum CO₂partial pressure (ppCO₂) observed during regeneration of the sorbent atthe indicated temperature in a regeneration gas having a CO₂ partialpressure of 15 psia. These results indicate the maximum CO₂ partialpressure that can be realized in the regeneration off-gas at theprescribed temperature. The maximum CO₂ partial pressure that can berealized during sorbent regeneration was found to decrease from 450° C.to 410° C. At 410° C., the sorbent was found to not regenerate at alland therefore, the maximum CO₂ partial pressure in the regenerationoff-gas is less than 15 psia CO₂. These results indicate that the Mg—Nasorbent of Example 1 can be regenerated by in a partial pressure swingprocess combined with a negative temperature swing.

TABLE 1 Regeneration Max. ppCO₂ Temperature [° C.] [psia] 450 44.0 44038.0 430 19.5 420 17.0 410 ≤15.0   Sorbent loaded at 450° C. in 150 psiaCO₂. Total pressure: 300 psia. ppCO₂ = CO₂ partial pressure

Example 7: Effect of Alkali Element on Sorbent Performance

The effect of the alkali element in the mixed salt sorbent was evaluatedby preparing sorbents with the first three alkali earth metals in thePeriodic Table of the Elements, specifically: Lithium (Li), Sodium (Na),and Potassium (K). The mixed salt sorbents were prepared following thesame co-precipitation preparation and having the same Mg:Alkali Metalmolar ratio of 1:6. The prepared sorbents were evaluated for the removalof CO₂ from simulated exhaust gas in a fixed-bed reactor system at theexperimental conditions (temperature, gas composition, and gas hourlyspace velocity (GHSV)) provided in Table 2 below.

TABLE 2 Absorption Temperature: 100 to 450° C. Gas Composition: 13% CO₂,13% H₂O, Bal. N₂ GHSV: 3,125 h⁻¹ Regeneration Temperature: Ramp to 450°C. at 10° C./min Gas Composition: N₂ GHSV: 2,500 h⁻¹

The effect of the alkali element on the performance of the mixed saltsorbent is illustrated in FIG. 6. These results suggest that theselection of the alkali element (e.g., Li, Na, K) can be used to tunethe sorbent's window of operation. From these results, it appears thatsorbents containing sodium (Na) provide the best operational temperaturerange for many applications, and such sorbents are also capable ofachieving the highest CO₂ loading. However, sorbents containing Li or Kwere also shown to absorb carbon dioxide. The sorbent containing sodiumabsorbed CO₂ over a temperature range of about 100° C. to about 425° C.,reaching a maximum at about 350° C. The sorbent containing lithium wasmost effective at 200° C. and showed absorption of CO₂ over atemperature range of about 200° C. to about 275° C., while the compoundcontaining potassium absorbed CO₂ at a higher temperature ranging fromabout 300° C. to about 425° C. with a peak at about 350° C.

Example 8: Effect of Magnesium Source on Sorbent Performance(Co-Precipitation Method)

One of the preparation parameters that can affect the composition andperformance of the sorbent is the source of magnesium, which can affectthe salt species formed during precipitation. Since magnesium carbonateor magnesium oxide is the targeted magnesium compounds in the saltmixture, selection of the magnesium source that preferentially leads tothe formation of these species is desired. In this study, the effect ofthe magnesium source of the performance of the mixed salt sorbent wasevaluated by preparing sorbents from magnesium nitrate (Mg(NO₃)₂),magnesium oxide (MgO), and magnesium hydroxide (Mg(OH)₂). These sorbentswere prepared following the same co-precipitation preparation procedurewith a Mg:Na molar ratio of 1:6. The prepared sorbents were evaluatedfor the removal of CO₂ from simulated exhaust gas in a fixed-bed reactorsystem at the same experimental conditions (temperature, gascomposition, and gas hourly space velocity (GHSV)) used in Example 7.

The effect of the magnesium source on the CO₂ loading as a function oftemperature for the mixed salt sorbents is provided in FIG. 7. As can beseen, the sorbent prepared from magnesium nitrate achieved significantlygreater CO₂ loadings than the oxide or hydroxide sorbents, indicatingthat the magnesium source has a significant impact on the performance ofthe sorbent. However, all three tested magnesium salts produced asorbent that absorbed carbon dioxide. The primary difference betweenthese magnesium sources is the solubility of the salt in water. Forexample, the solubility of magnesium nitrate in water is 125 g/100 ml,whereas the solubility of magnesium hydroxide is 1.2 mg/100 ml.

Although not bound by any particular theory of operation, although thesame preparation procedure was followed, it appears that the resultingsorbent materials were formed via different pathways. The magnesiumnitrate-prepared mixed salt was likely formed by the addition of asolution of sodium carbonate (Na₂CO₃) to a solution containingcompletely dissolved magnesium nitrate. Upon the addition of sodiumcarbonate, a white precipitate, the mixed salt, was formed.Precipitation likely occurred due to anion exchange between themagnesium and sodium cations in which a mixture of magnesium carbonate,hydroxide, and nitrate and sodium nitrate and carbonate was formed.

The sorbents made using magnesium oxide and hydroxide likely followed adifferent pathway due to their limited solubility in water. Followingthe same procedure, a solution containing sodium carbonate was slowlyadded to a solution containing a well-mixed slurry of magnesiumhydroxide. Due to the presence of a precipitate, it was not possible toobserve or distinguish the precipitation of a mixed salt species.

The CO₂ loading results indicate that the magnesium source, andspecifically the solubility of the source compound in water, is a veryimportant parameter in the preparation of a mixed salt sorbent with highCO₂ loading capacity. Although sorbent prepared using magnesium nitrateexhibited very good CO₂ loading capacity, other highly water solublemagnesium salts, such as magnesium chloride (54.3 g/100 ml) andmagnesium acetate (39.6 g/100 ml), would also be useful for producingsorbents of the invention.

Example 9: Effect of Mg:Na Molar Ratio on Sorbent Performance

It is understood that CO₂ is loaded on the sorbent of the invention inthe form of MgCO₃, which has been verified by XRD, and that the sodiumspecies, although clearly involved in the CO₂ capture mechanism, do notstore CO₂. Therefore, to more thoroughly understand the role of sodiumin the CO₂ capture mechanism in the mixed salt sorbent, several sorbentsamples were prepared with Mg:Na molar ratios in the reagent mixtureranging from 1:3 to 1:8. The sorbents were prepared following the sameco-precipitation preparation procedure with the exception of thequantity of Na₂CO₃ used during the precipitation stage. The preparedsorbents were evaluated for the removal of CO₂ from simulated exhaustgas in the fixed-bed reactor system at the same experimental conditions(temperature, gas composition, and gas hourly space velocity (GHSV))used in Example 7.

The experimental results presented in FIG. 8 indicate that the Mg:Namolar ratio does affect the CO₂ loading of the sorbent. For sorbentspreparing using molar excesses of sodium (e.g., 1:6 and 1:8), theperformance of the sorbent is consistent with previous findings. The CO₂loading capacity increases with absorption temperature, passes through amaximum of approximately 13 wt % CO₂ at 350° C., and rapidly decreaseswith increasing absorption temperature. Increasing the sodium molarexcess from 6 to 8 appears to have little effect on the general shape ofthe absorption curve. The peak CO₂ loading is approximately 12 wt % at350° C. for both materials, and both exhibit rapid decrease in CO₂loading with increasing temperature. The only observable difference is aslight decrease in the CO₂ loading for temperatures below 350° C. forthe sorbent with a larger quantity of sodium.

Decreasing the sodium content to 1:4 and below (e.g., 1:3) appears tosignificantly affect the CO₂ loading profile. Although, the sorbenthaving an equimolar Mg:Na ratio achieved the lowest CO₂ loading of thesorbents evaluated, it exhibited peak loading at 250° C. Thus,decreasing the sodium content of the sorbent to a Mg:Na ratio of 1:3resulted in a significant increase in CO₂ loading at 250° C. Shiftingthe peak CO₂ loading from 350° C. to 250° C. by reducing the sodiumcontent of the sorbent is a significant and promising finding. Thisfinding suggests that CO₂ interacts with the mixed salt sorbent viadifferent mechanisms, and that the mechanism and ultimately the windowof operation can be affected by adjusting the composition.

Example 10: Effect of Precipitation Solution Concentration on SorbentPerformance

One of the preparation parameters that can affect the performance of thesorbent is the concentration of the precipitating solution. In thisstudy, mixed salt sorbents having the same composition at fourprecipitation solution concentrations (0.05, 0.1, 0.2, and 0.3M) wereprepared. These sorbents were prepared following the sameco-precipitation preparation procedure with a Mg:Na molar ratio of 1:6.The prepared sorbents were evaluated for the removal of CO₂ fromsimulated exhaust gas in a fixed-bed reactor system at the sameexperimental conditions (temperature, gas composition, and gas hourlyspace velocity (GHSV)) used in Example 7.

The effect of the precipitation solution concentration on the CO₂loading as a function of temperature for the mixed salt sorbents isillustrated in FIG. 9. The concentration of the precipitation solutionhas a significant effect on the performance of the sorbent. Decreasingthe concentration of the precipitating solution results in a lowering ofthe peak loading temperature from 350° C. to between 250 and 275° C. Inaddition to shifting the peak loading temperature, the quantity of CO₂loaded increased from 12 wt % to approximately 20 wt %. The performanceof the sorbents prepared from low concentration solutions isparticularly interesting, as those sorbents achieved both greater CO₂loading and peak loading at lower temperatures.

Example 11: Effect of Precipitating Agent on Sorbent Performance

This study evaluated the role of the precipitating agent on theperformance of the mixed salt sorbent. Two precipitating agents wereevaluated: sodium carbonate (Na₂CO₃) and ammonium carbonate ((NH₄)₂CO₃).The samples were prepared using slightly different co-precipitationtechniques. The first sample was prepared by slowly adding a solution ofsodium carbonate to a solution of magnesium nitrate. The second samplewas prepared by slowly adding a solution of ammonium carbonate to amixture of magnesium nitrate and sodium nitrate. These sorbents wereprepared with a Mg:Na molar ratio of 1:6. The prepared sorbents wereevaluated for the removal of CO₂ from simulated exhaust gas in afixed-bed reactor system at the same experimental conditions(temperature, gas composition, and gas hourly space velocity (GHSV))used in Example 7.

The effect of the precipitating agent on the CO₂ loading as a functionof temperature for the Mg-Alkali mixed salt sorbents is provided in FIG.10. The performance of the prepared materials is significantlydifferent. The sodium carbonate prepared material exhibits a broadabsorption curve, whereas the ammonium carbonate prepared sorbent has anarrower temperature range over which absorption of CO₂ was observedwith a sharp spike appearing at about 300° C. These results suggest thatthe precipitating agent has an effect on the performance of the mixedsalt sorbent, which may be useful to exploit for specific applicationsrequiring a narrow absorption temperature range.

Example 12: Compositional Analysis of Sorbents Prepared byCo-Precipitation Method

Several mixed salt sorbent compositions were prepared at differentprecipitation solution concentrations according to the general processset forth in Example 2. A combination of inductively coupled plasma(ICP) analysis and elemental analysis (CHONS) was used todetermine/estimate the molecular species composition of each prepared,co-precipitation sorbent. The weight percentages of each component ofthe sorbents were estimated by combining results from these analyses andthe results are present in Table 3 below. Results indicated thatreducing the co-precipitation concentration (0.2 M→0.05 M) resulted in ahigher MgO content in the sorbent and a decrease in the NaNO₃ content.It should be noted that the sorbent materials were prepared at aconstant pH.

TABLE 3 Sample MgO Na₂CO₃ NaNO₃ 0.05M 84.59 14.12 1.29  0.1M 81.72 12.086.20  0.2M 75.81 15.99 8.02

Example 13: Comparison of Performance of Sorbent Produced byCo-Precipitation Process and Gelation/Colloid Process

A mixed salt sorbent of the invention was prepared having the samecomposition as the 0.05 M sample shown in Table 3 above using both theco-precipitation method and the gelation/physical mixing method setforth herein, and evaluated for CO₂ capture performance at theconditions given in Example 7. The effect of preparation method on theCO₂ capture performance of the sorbent, having the same elementalcomposition, is provided in FIG. 11. It is evident that the two sorbentshave very similar CO₂ loading curves, with both materials achievingapproximately 20 wt % CO₂ loading at 275° C. to 300° C., with a veryrapid decrease in loading with increasing absorption temperature. Thesimilarity in the CO₂ loading curves indicates that the sorbentsprepared by different preparation techniques have very similar CO₂capture properties and that the desired characteristics of thebest-performing sorbent prepared by co-precipitation can be retainedwhen prepared by the physical mixing/gelation method.

Example 14: Effect of Magnesium Source on Sorbent Performance (GelationMethod)

As noted in Example 1, basic magnesium carbonate (magnesium carbonatehydroxide) was the MgO source in the gelation/physical mixture sorbent.One issue with basic magnesium carbonate is that it has very low bulkdensity and is more expensive than commercially-available magnesiumoxide. Two physical mixture samples were prepared using powdered MgO andnano-MgO as the MgO source having the same composition as the sorbentprepared using basic magnesium carbonate in Example 1 to determine ifless expensive, commercially-available magnesium oxides can be used.These sorbents were evaluated for CO₂ capture performance at theconditions given in Example 7.

The magnesium source was found to have a significant effect on CO₂loading capacity of the mixed salt sorbent, as seen by results presentedin FIG. 12. The sorbents prepared with magnesium oxide were unable toachieve a CO₂ loading in excess of 5 wt % CO₂ and showed a decreasingCO₂ loading capacity with increasing absorption temperature. TheMgO-based materials did not show the characteristic “volcano” shape thatwas observed for the mixed salt sorbent. From these results, it appearsthat basic magnesium carbonate should be used as the magnesium source inthe gelation process.

Example 15: Effect of Drying Method on Sorbent Performance

Two drying methods were evaluated for drying the wet sorbent materialformed in the production method to determine if the drying methodaffects the performance of the sorbent. The two tested methods were: 1)oven drying of a wet filter cake; and 2) direct spray drying of thesorbent material. Two sorbent batches having the same composition wereprepared via the spray dryer and filtering/oven drying methods. The CO₂capture performance of each sorbent was evaluated at the experimentalconditions given in Example 7.

The CO₂ capture performance of the sorbent prepared via the spray dryingand filtering/oven drying methods are presented in FIG. 13. Theseresults clearly indicate that the spray drying method yields a superiorCO₂ capture sorbent. The spray-dried material exhibited ˜5 wt % higherCO₂ loading at all capture temperatures <300° C., compared to thefilter/oven dried material. However, the filtered/oven dried sorbentexhibited very good CO₂ performance as well, achieving ˜18 wt % CO₂loading at 300° C.

Many modifications and other embodiments of the inventions set forthherein will come to mind to one skilled in the art to which theseinventions pertain having the benefit of the teachings presented in theforegoing descriptions and the associated drawings. Therefore, it is tobe understood that the inventions are not to be limited to the specificembodiments disclosed and that modifications and other embodiments areintended to be included within the scope of the appended claims.Although specific terms are employed herein, they are used in a genericand descriptive sense only and not for purposes of limitation.

The invention claimed is:
 1. A method for removing carbon dioxide from a gaseous stream, comprising contacting a gaseous stream containing carbon dioxide with a sorbent material comprising a mixed salt composition in solid form comprising: i) magnesium oxide; ii) an alkali metal carbonate; and iii) an alkali metal nitrate, wherein the composition has a molar excess of magnesium characterized by a Mg:X atomic ratio of at least about 1.1:1, wherein X is the alkali metal.
 2. The method of claim 1, wherein the contacting step occurs at a temperature of about 100° C. to about 450° C.
 3. The method of claim 1, wherein the contacting step occurs at a temperature of about 250° C. to about 375° C.
 4. The method of claim 1, wherein the carbon dioxide pressure in the gaseous stream is about 1 to about 300 psia.
 5. The method of claim 1, wherein the carbon dioxide pressure in the gaseous stream is less than about 5 psia.
 6. The method of claim 1, wherein the sorbent material is contained within a fixed bed or fluidized bed absorber.
 7. The method of claim 1, wherein the sorbent material exhibits a CO₂ loading of at least about 10 weight percent CO₂ at an absorption temperature of about 250 to about 350° C.
 8. The method of claim 1, wherein the alkali metal comprises sodium.
 9. The method of claim 1, wherein the Mg:X atomic ratio is at least about 4:1.
 10. The method of claim 1, wherein the Mg:X atomic ratio is at least about 6:1.
 11. The method of claim 1, wherein the alkali metal nitrate is present in an amount of at least about 1% by weight, based on total dry weight of the mixed salt composition.
 12. The method of claim 1, wherein the mixed salt composition comprises MgO:Na₂CO₃:NaNO₃, wherein the atomic ratio of Mg:Na is at least about 1.1:1.
 13. The method of claim 1, wherein the mixed salt composition has a crush strength in pellet form, as determined by the Shell method, of at least about 0.3 MPa.
 14. The method of claim 1, further comprising the step of regenerating the sorbent material using pressure-swing absorption, vacuum-swing absorption, temperature-swing absorption, or a combination thereof to cause desorption of carbon dioxide.
 15. The method of claim 14, wherein the regenerating step comprises at least one of raising the temperature of the sorbent material and lowering the pressure applied to the sorbent material, as compared to the temperature and pressure during the contacting step. 